The present invention relates to an organosilicon material with ladderlike or tube-like structure and the method for producing the same, particularly the present invention relates to an organo-bridged ladderlike polysiloxane, tube-like organosilicon polymers, complexes thereof and the method for producing the same.
Polysiloxanes having a ladderlike structure have been widely used as the parts of electronic instruments, protection layer and interlayer insulation materials for semiconductors, pellicle materials, paint materials and the like, since they have excellent mechanical properties, and are excellent in heat resistance and electrical insulation.
Brown, J. F. (J. Am. Chem. Soc., 1960, 82, 6194) reported polyphenylsilsesquioxane with ladderlike structure. Japanese Patent No. 25061/1985(JP-B-60-25061), No. 36983/1989 (JP-B-1-36983) and No. 274056/1991(JP-A-3-274056) disclosed a photosensitive silicon resin composite comprising a ladderlike polysiloxane having an alkyl group, a phenyl group, a vinyl group, an allyl group and the like. Japanese Patent laid-open No.105881/1990 (JP-A-2-105991) disclosed a composite for forming a film comprising a hydroxy-terminated ladderlike polysiloxane having an alkyl group or a phenyl group and having a number-average molecular weight of 2000 to 5000.
However, it is difficult to obtain a high molecular weight polysiloxane with a ladderlike skeleton by using the methods described in the above publications. As is disclosed in the above applications, with the growing of the molecular weight of the ladderlike polysiloxane, the ladderlike skeleton in the polysiloxane tends to break and branch, resulting insolubility in organic solvents.
Especially, in the methods of above publications, trichlorosilanes having an alkyl group, an aralkyl group, or a phenyl group, which are unreactive or inert to hydrolysis(e.g., methyltricholorosilane and phenyltrichlorosilane) are used.
Chinese patent No. CN 94 1005071 disclosed highly regulated ladderlike hydrogen polysilsesquioxanes and copolymers and their preparation. In addition, there have been reported a highly regulated ladderlike reactive vinyl- or allyl-polysilsesquioxanes (React. Polym., 1999, 39, 1). Japanese Patent No. JP 08188649 disclosed highly regulated ladderlike polysilsesqioxanes and copolymers containing reactive groups and their preparation. They were synthesized via pre-coupling and stepwise hydrolysis, condensation by using organosilicon monomers containing reactive groups, such as trichlorosilane, vinyltrichlorosilane, allyltrichlorosilane, alkoxytrichlorosilane and the like as starting materials, and employing xcex1,xcfx89-diamine as the coupling reagent. They have the following structure. 
wherein R and Rxe2x80x2 can be the same or different, and are selected from the family consisting of hydrogen, alkyl, alkoxyl, aryl such as phenyl and biphenyl, and alkenyl such as vinyl, allyl.
As described in the above-mentioned Chinese patent No. CN 941005071 and Japanese patent No. JP 08188649, the highly regulated ladderlike polysilsesquioxanes prepared via precoupling with xcex1,xcfx89-diamine as coupling agent, hydrolysis and polycondensation have a high solubility and excellent film-forming ability, moreover, the gelification accompanied with growing molecular weight of the polymer as described in the earlier applications can be inhibited.
Especially, in the method described above, trichlorosilanes having reactive groups, such as hydrogen, vinyl and allyl, alkoxy groups etc can be used, because the reaction conditions are very mild. The resulted ladderlike polymers have reactive side chains, which can be used to produce different functional derivatives. The ladderlike polysiloxane possesses cis-isotactic configuration (Materials Science and Engineering, C 10, 1999, 13-18).
In the methods described in the above-mentioned Chinese patent No. CN 941005071 and Japanese patent No. JP 08188649, the first step is preamminolysis of trichlorosilane with xcex1,xcfx89)-diamine to obtain an intermediate represented by the following formula(II): 
wherein X represents a halogen atom (Cl, Br, I), Y represents a diamine residue. R is hydrogen, alkyl, alkenyl, aryl or other substituting groups. During hydrolyis and polycondensation the bridged diamine residue is gradually removed. That means the diamine residue exists in the intermediate compound only plays a role of temporary bridge.
According to the method as mentioned above, highly regulated ladderlike polysiloxane comprises a fixed Sixe2x80x94Oxe2x80x94Si bridge in the ladder skeleton. So the dimension and affinity of ladder rung are limited.
Known tube-like polymers includes, for example, those reported by S. Lijima in 1991(Nature, 1991, 354, 56), in which the preparation and structure of nano-scale carbon tubes having poor solubility in organic solvent is described. In 1995, H. Nakamura et al reported a tube-like polymer prepared by using siloxane gel as starting material. However the polymer is neither soluble nor meltable. In 1993, A. Harada et al reported the formation of tube-like organic polymers by using naturally occuring cyclodextrins as the starting materials (Nature, 1993, 364, 576). Because the dimension and the shape of the cyclodextrin unit are fixed, the diameter and chemical affinity of the tube-like polymers are also fixed and difficult to control. For the above reasons, the applications of these tube-like polymers are limited.
There have been reported a supermolecular complex based on tube-like cyclodextrins as host molecule (Nature, 1993, 364, 76). In such supermolecular complex, the pore diameter of the tube and chemical affinity of the cavity can not be readily adjusted, therefore, the guest molecules to be entrapped inside the tube are limited. Entrapment of metal ions or metal oxide molecules inside a nano-scale carbon tube to form the supermolecular complex has also been reported (Chem. Commun., 1995, 1335). However the preparation involves complicated steps and severe reaction conditions. In addition, the selectivity of entrapment was very poor. Further, entrapment of polyaniline inside the tube of V2O5 gel to form supermolecular complex has been reported (J. Am. Chem. Soc., 1989, 111, 4319). This complex showed electrical conductivity. However, since this supermolecular complex forms a cross-linked system, it is, neither soluble nor meltable, thus can not be reprocessed. In addition, the selectivity of entrapment was very poor too.
Chinese patent No. CN 9712236.9 (1997, 1) disclosed xe2x80x9ctube-like organosilicon polymer and a method for producing the samexe2x80x9d. The tube-like organosilicon polymer can be prepared in (1+1) mode or (2+2) mode of tubing reaction. The (1+1) mode means that a coupling reaction of one kind of cis-isotactic reactive ladderlike polysilsesquioxane with another kind of cis-isotactic reactive ladderlike polysilsesquioxane. The (2+2) mode means that two parts of one kind of cis-isotactic reactive ladderlike polysilsesquioxane with two parts of low molar mass coupling agents. Because the tube-like polymer is resulted from the above-mentioned ladderlike polysiloxane having fixed Sixe2x80x94Oxe2x80x94Si bridge, so the dimension, shape and chemical affinity of the tube-like organosilicon polymer are also limited. And also the guest molecules that can be entrapped inside the tube are limited.
The present invention is directed to solving the problems of the limited dimension and chemical affinity associated with the above-mentioned fixed Sixe2x80x94Oxe2x80x94Si bridged ladderlike polysilsesquioxanes and tube-like polymers derived therefrom.
It is an object of the present invention to provide an organo-bridged ladderlike polysiloxane, which is characterized by:
(1) having an adjustable organo-bridged ladder rung which can play a templating role, namely, the length of the ladder rung varies in the range of 5-50 xc3x85, and its chemical affinity can be adjusted;
(2) having terminal groups that can play a prefixation role such as hydroxy, carboxylic, amino amid and the like;
(3) having a cis-isotactic configuration and a high regularity (more than 80%);
(4) having a mono-dispersed molecular weights distribution in the range of 103-106 Dalton;
(5) having reactive side groups such as hydrogen, halogen-containing group, alkenyl, substituted alkenyl, alkynyl, substituted alkynyl, aryl, or the like.
It is yet another object of the present invention to provide a method for producing the above-mentioned organo-bridged ladderlike polysiloxane.
It is a further object of the present invention to provide an organosilicon tube-like polymer obtained from the above-mentioned organo-bridged ladderlike polysiloxane and the producing method thereof.
It is still a further object of the present invention to provide a supermolecular complex obtained from the above-mentioned tube-like organosilicon polymer as host molecule and guest molecules entrapped inside the tube-like organosilicon polymer based on the dimension, shape and affinity of tube-like polymer, and the producing method thereof.
The organo-bridged ladderlike polysiloxane of the present invention is represented by the following formula: 
wherein,
n is an integer from 10 to 105, R is a reactive group selected from the group consisting of hydrogen, halogen-containing group, alkenyl, substituted alkenyl, alkynyl, substituted alkynyl, aryl, substituted aryl, xe2x80x94C6H4OH, xe2x80x94C6H4NH2, xe2x80x94C6H4N2+Clxe2x88x92 and xe2x80x94C6H4xe2x80x94C6H4N2+Clxe2x88x92; R1 is selected from the group consisting of a hydrogen-bonding producing group, a charge-transfer complex producing group, a metal ion-ligand complexes producing group, and an electrostatic interaction group; 
xe2x80x83is one or more organo-bridged groups presented by the following formula: 
xe2x80x83wherein
X is a carbon or a nitrogen atom, and
when X is a nitrogen atom, Y is absent; Z is also absent; each of L1 and L2 is a hydrogen atom; m is 1; n is, 2, 3, 4, or 5;
when X is a carbon atom, Y is absent or is selected from the group consisting of xe2x80x94CONHxe2x80x94, xe2x80x94COCH2COxe2x80x94, and xe2x80x94COOxe2x80x94; Z is absent or is selected from the group consisting of xe2x80x94Oxe2x80x94, xe2x80x94NHxe2x80x94, xe2x80x94CONHxe2x80x94, xe2x80x94COCH2COxe2x80x94, xe2x80x94COOxe2x80x94; L1 and L2 may be same or different and is selected from the group consisting of xe2x80x94H, xe2x80x94OH, xe2x80x94NH2, and xe2x80x94CONH2; m is 0, 1, or 2; n is 0, 1, 2, 3, 4 or 5.
In the organo-bridged ladderlike polysiloxane of the present invention, R1 is preferably selected from the group consisting of hydroxy, nitro, amino, amide, quaternary ammonium cation, phenolic and carboxylic anions.
In the organo-bridged ladderlike polysiloxane of the present invention, the organo-bridged group or organo-bridged groups are preferably one of the following: 
The above ladder rung can be divided into the following four categories:
(1) Hydrogen-bonding producing groups comprising hydroxy, amino or amide groups.
(2) Metal ion-ligand complexes producing groups consisting of the metal ions having square-planner coordination configuration such as cupric, palladic, nickelous cations or the like, and the coordinating ligand such as aromatic xcex2-diketone, imine, azo-groups or the like.
(3) Charge-transfer complex producing groups consisting of the electron-donating groups such as hydroxy, amino, quinone, phenolic anion and carboxylic anions or the like, and the electron-accepting groups such as nitro, cyano, quinone, quaternary ammonium cation, phosphonium cation or the like.
(4) Electrostatic interaction producing groups consisting of the cations such as quaternary ammonium or a phosphonium cation and the anions such as carboxylic anion or phenolic anions or the like.
The above mentioned terminal group R1 can also be divided into the following four categories:
(1) A hydrogen-bonding producing group such as a hydroxy, carboxylic, amino or amide group.
(2) A charge-transfer complex producing group consisting of a electron-donating group such as hydroxy, amino, hydroquinone, phenolic anion or a carboxylic anion and a electron-accepting group such as a nitro, cyano, quinone, quaternary ammonium cation or the like.
(3) A metal ion-ligand complex producing group consisting of a metal ion having square-planner coordination configuration such as cupric, palladic, nickelous cation or the like, and a coordinating ligand such as aromatic xcex2-diketone, imine, azo-group or the like.
(4) An electrostatic interaction group consisting of a cation such as quaternary ammonium anion phosphonium anion and a anion such as carboxylic anion or phenolic anion or the like.
The ladderlike polysiloxane possesses cis-isotactic configuration. Its structural regularity is more than 80%. The molecular weight distribution is mono-dispersed and varies in the range of 103-106. The length of the ladder rung is adjustable and varies in the range of 5-50 xc3x85.
The present invention also relates to improving the structural regularity of the organo-bridged ladderlike polysiloxane. The method involves introducing the self-assembly into the polymerization process by using the above-mentioned organo-bridged ladder rung as template. Via the template interaction between the adjacent ladder rungs, the organosilicon monomers are well-oriented and self-assembled before polymerization takes place. Thus an ordered architecture can be formed during the polymerization process. It leads to high regularity of the ladderlike polysiloxanes of the present invention. The template interactions between the ladder rungs mentioned in the present invention include (1) hydrogen-bond effect (2) charge-transfer interaction (3) metal ion-ligand interaction (4) electrostatic interaction.
In another aspect of the present invention, there is provided a method for preparation of the organo-bridged ladderlike polysiloxane of the present invention, comprising the steps of:
1. Synthesis of the Organosilicon Monomer Containing Organo-bridged Group
(1) synthesizing the organo-bridged organosilicon monomer by a coupling reaction of trihalogensilane or trialkoxysilane with xcex1,xcfx89-difunctional coupling agent, the monomer being represented by 
(2) hydrolysing the above-mentioned organo-bridged organosilicon monomer to obtain an intermediate compound represented by 
(3) polycondensing the above-mentioned hydrolysis product to obtain an organo-bridged ladderlike polysiloxane represented by 
(4) end-capping the above-mentioned organo-bridged ladderlike polysiloxane with functional organosilicon compound to obtain the end-capped organo-bridged ladderlike polysiloxane represented by 
(5) carrying out fractional precipitation to obtain a mono-dispersed organo-bridged ladderlike polysiloxane
wherein,
X is halogen atom or alkoxy group; R is a reactive group selected from the group consisting of hydrogen, halogen-containing group, alkenyl, substituted alkenyl, alkynyl, substituted alkynyl, aryl, substituted aryl, xe2x80x94C6H4OH, xe2x80x94C6H4NH2, xe2x80x94C6H4N2+Clxe2x88x92 and xe2x80x94C6H4xe2x80x94C6H4N2+Clxe2x88x92; n is an integer from 10 to 105.
Specifically, the method of the present invention includes the following steps:
(1-1) Synthesizing the Organosilicon Monomer by Hydrosilylation Reaction
One of the alkenyl- or alkynyl-terminated compound having the following formula 
is dissolved in tetrafuran (THF). Under the argon atmosphere platinum compound catalyst is added into the THF solution. After stirring the mixture for 30 minutes at room temperature, another compound containing hydrosilyl group is added. The molar ratio of the alkenyl- or alkyl-terminated compound to hydrosilane is 1:2-1:6. The above mixture is stirred at 40xc2x0 C. for 24-48 hours and then the organo-bridged organosilicon monomer is obtained. It is represented by following formulas: 
wherein R represents a reactive groups such as alkyl, substituted alkyl or the like. X represents a halogen atom (Cl, Br, I) or a alkoxy group such as a methoxy or a ethoxy group.
The platinum compound catalyst used in the present invention for hydrosilylation reaction includes Cp2PtCl2, H2PtCl6 and complexes thereof.
The molar ratio of the platinum catalyst to alkenyl-terminated compound or alkynyl-terminated compound in the present invention is 10xe2x88x926-10xe2x88x924.
(1-2) Synthesizing the Organosilicon Monomer by Condensation Reaction
Under argon atmosphere, a solution of xcex1,xcfx89-difunctional compound such as xcex1,xcfx89-diphenol 
in THF (0.2-0.8 mmol/mL) is added dropwise into the THF solution containing organotrichlorosilane and pyridine used as the hydrochloride-absorbing agent. The molar ratio of xcex1,xcfx89-diphenol to the alkenyltrichlorosilane is 1:2-1:6. The reaction system is stirred at the refluxing temperature for another 1-5 hours. After the reaction is completed, the pyridine hydrochloride salt is filtered off. The filtrate is vacuum-distilled and then a organo-bridged silicon monomer is obtained. Its chemical structure is represented by the following formulas: 
wherein R represents a reactive groups such as alkenyl, a substituted alkenyl, alkynyl, substituted alkynyl, X represents halogen atom (Cl, Br, I) or alkoxy group.
2. Hydrolysis of the Organo-bridged Organosilicon Monomer
The above-mentioned organosilicon monomer is dissolved in a mixed solvent, such as toluene and acetone or THF. The volume ratio of toluene to acetone or THF is 1.5:1-4:1. The concentration of organosilicon monomer is 0.05-0.3 mmol/mL. A solution of water in acetone or THF is added dropwise into the above mixed solvent. Then the reaction mixture is stirred at room temperature for 3-6 hours.
3. Polycondensation of the Hydrolysis Product
A catalysts such as sulfuric acid or triethylamine and water-adsorbing agent such as anhydrous sodium sulfate or molecular sieve (4 xc3x85) are added into the above-mentioned hydrolyzed solution. After stirring the solution at 50xc2x0 C. for 1-5 days, the solution is washed with distilled water until neutralized, then dried over anhydrous sodium sulfate or the molecular sieve and further stirred at 40-60xc2x0 C. for 1-5 days.
4. End-capping the Ladderlike Polymer
The above-mentioned condensation product should be treated with different kinds of capping agents possessing functional groups to produce hydrogen bonding, charge transfer complex, metal ion-ligand complex, electrostatic interactions. Thus, for example, after the condensation reaction is completed, the resulted solution is washed with distilled water until neutralized and dried over anhydrous sodium sulfate or molecular sieve, then pyridine is added. A solution of dimethyldichlorosilane in toluene (concentration: 0.1 mol/L) is added dropwise under stirring into the above solution. The molar ratio of end-capping agent of dimethyldichlorosilane to the organosilicon monomer in the present invention is in the range of 1xc3x9710xe2x88x927-1xc3x9710xe2x88x921. The reaction mixture is further stirred at room temperature for 8 hours. The pyridine hydrochloride formed is filtered out and the resulted solution is washed with distilled water until neutralized and dried over anhydrous sodium sulfate or molecular sieve.
5. Fractional Precipitation of the Ladderlike Polymer
The above-mentioned toluene solution of organo-bridged ladderlike polysiloxane is subject to fractionation precipitation with methanol to obtain the mono-dispersed ladderlike organo-bridged polysiloxane.
The main properties of the organo-bridged ladderlike polysiloxanes of the present invention are listed in Table 1.
The organo-bridged ladderlike polysiloxane of the present invention is highly regulated. Its skeleton dimension and chemical affinity are adjustable. It is highly soluble in organic solvents. Thus, it has potential applications in inorgno-organo hybrid materials, nonlinear optical materials, electronic materials, organosilicon tube-like polymers, and supramolecular complexes.
The present invention further provides a tube-like organosilicon polymer derived from the organo-bridged ladderlike polysiloxane of the present invention, which is represented by the following formula: 
wherein  is the bridge group connecting two main chains of ladderlike polymers. This group includes xe2x80x94(CH2)3SiOSi(CH2)3xe2x80x94, xe2x80x94C6H4Nxe2x95x90NC6H4xe2x80x94, xe2x80x94(CH2)mSi(CH3)2C6H4OC6H4(CH3)2Si(CH2)mxe2x80x94(m=2,3) and the like
wherein  is the organ-bridged ladder rung of the ladderlike polymer itself, which has the same definition with the organ-bridged group mentioned above.
In a further aspect of the present invention, there is provided a method for preparing the tube-like organosilicon polymer of the present invention. The organo-bridged ladderlike polysiloxanes can be formed through one of the following three procedures: 1) Via intra-macromolecular cyclization of the organo-bridged ladderlike polysiloxane having reactive side groups; 2) In (1+1) mode of coupling reaction between two organo-bridged ladderlike polysiloxanes having reactive side groups; 3) In (2+2) mode of coupling reaction between two organo-bridged ladderlike polysiloxanes with the same reactive side groups and the coupling reagents.
Specifically, the tube-like organosilicon polymer of the present invention is prepared by the following method:
1) Via intra-macromolecular cyclization using above-mentioned organo-bridged ladderlike polysiloxane having reactive side groups as the starting materials:
The above-mentioned intra-macromolecular cyclization includes the following types: (1) hydrosilylation cyclization reaction; (2) diazo coupling cyclization reaction; (3) Ulman or Grignard coupling cyclization reaction.
(1-1) Hydrosilylation cyclization reaction
The organo-bridged ladderlike polysiloxane having xe2x80x94CHxe2x95x90CH2 or xe2x80x94CH2xe2x80x94CHxe2x95x90CH2 side groups is dissolved in dried solvent. Under the inert gas atmosphere the above ladderlike polysiloxane is added into a reaction vessel. Solvent, Pt compound catalyst and trichlorosilane or trimethoxysilane or triethoxysilane are added to the reaction mixture. The concentration of reactants are in the range of 5xcx9c40 mg/mL. The molar ratio of ladderlike polysiloxane to trichlorosilane (or trimethoxysilane or triethoxysilane) is 1:0.8 to 1:1.5. The reaction is carried out at 40xcx9c100xc2x0 C. for 12xcx9c72 hours. After the reaction is completed, a solution of xcex1,xcfx89-diamine and triethylamine is added to the reaction mixture at xe2x88x925xcx9cxe2x88x9215xc2x0 C. in 4 hours. Then a water-containing solution is added dropwise at xe2x88x925xcx9cxe2x88x9210xc2x0 C. over 5 hours. After addition, the reaction mixture is gradually warmed to room temperature and kept stirring for another 10 hours. After removal of salts, the residue solution is dried over anhydrous Na2SO4. The molar ratio of trichlorosilane (or trimethoxysilane or triethoxysilane) to xcex1,xcfx89-diamine and to triethylamine is 1:1:2. The molar ratio of trichlorosilane (or trimethoxysilane or triethoxysilane) to water is 1:2. The polycondensation process is carried out using Me4NOH as catalyst. The solution was stirred at 50xcx9c90xc2x0 C. for 36xcx9c144 hours. Then the above solution is washed with aqueous solution of NaCl until neutralized and dried over anhydrous Na2SO4. After removal of solvent, a tube-like organosilicon polymer is obtained.
The Pt compound catalysts used for hydrosilylation cyclization reaction are H2PtCl6.6H2O or Cp2PtCl2 or their complexes.
The solvents that can be used in hydrosilylation cyclization reaction include toluene, xylene, ethylene glycol dimethyl ether, poly(allyl ether), dimethyl o-phthalate, 1,4-dioxane, tetrahydrofuran (THF), acetone, cyclohexanone or a mixture of above solvents. The amount of the solvent(s) is 50xcx9c500 mL/ per gram of ladderlike polysiloxane.
(1-2) Diazo coupling cyclization reaction
The organo-bridged ladderlike polysiloxane having both xe2x80x94C6H4OH and diazo side groups is dissolved in inorganic or a mixture of inorganic and organic solvents. The concentration is 30xcx9c45%. The above solution is added to the reaction mixture. The ice is added to the reaction mixture. The weight ratio of the ice to solvent is 1:3. Sodium acetate or acetic acid is added to the reaction mixture. The reaction is allowed to proceed at 0xcx9cxe2x88x925xc2x0 C. by ice-water. After the reaction, the reaction solution is extracted by diethyl ether. The ether solution was dried over anhydrous Na2SO4. After the removal of solvent, a tube-like organosilicon polymer is obtained.
The inorganic solvent or a mixture of inorganic and organic solvents used in the diazo coupling cyclization reaction include water, mixture of water and alcohol, mixture of water and pyridine or mixture of water and acetic acid and the like.
(1-3) Ulman or Grignard cyclization coupling reaction
The organo-bridged ladderlike polysiloxane having xe2x80x94C6H4C6H4C6H4I or xe2x80x94C6H4C6H4Br side groups is dissolved in dried organic solvents under argon atmosphere. The concentration is 1xcx9c10 wt. %. Then the above solution is added dropwise to the reaction mixture containing a Cu or Mg powder and a small amount of I2 at 0xcx9cxe2x88x925xc2x0 C. The molar ratio of ladderlike polysiloxane to Cu or Mg powders is 1:1-1:5. The reaction is allowed to proceed at 0xcx9cxe2x88x925xc2x0 C. by ice-water for 2xcx9c5 hours and then warmed up gradually till reflux for 5xcx9c9 hours. The reaction solution is extracted with hexane after cooling. Then the hexane solution is dried over anhydrous Na2SO4. After the removal of solvent, a tube-like organosilicon polymer is obtained.
The organic solvents can be used in the Ulman or Grignard cyclization reaction include toluene, xylene, ethylene glycol dimethyl ether, poly(allyl ether), dimethyl o-phthalate, 1,4-dioxane, tetrahydrofuran (THF), acetone, cyclohexanone or a mixture of above solvents.
2) In (1+1) mode of coupling reaction between the above-mentioned two organo-bridged ladderlike polysiloxanes having different reactive side groups.
3) In (2+2) mode of coupling reaction between two organo-bridged ladderlike polysiloxanes with the same reactive side groups and the coupling reagents.
The above-mentioned (1+1) or (2+2) mode of coupling reaction include the following types (1) hydrosilylation coupling reaction,: (2) diazo coupling reaction. (3) Ulman or Grignard coupling reaction and the like.
(1) Hydrosilylation coupling reaction
(1-1) In (1+1) mode of hydrosilylation coupling reaction, the synthetic procedure is as follows: Two organo-bridged ladderlike polysiloxanes having xe2x80x94CHxe2x95x90CH2 or xe2x80x94CH2xe2x80x94CHxe2x95x90CH2 side groups and Sixe2x80x94H side groups are dissolved in dried solvents, respectively. Then under the inert gas atmosphere they are added with the molar ratio of 1:0.8 to 1:1.5 into a reaction apparatus. Solvent and Pt catalyst are added to the reaction mixture. The concentration of reactants are in the range of 10xcx9c40 mg/mL. The reaction is allowed to proceed at 40xcx9c100xc2x0 C. for 12xcx9c72 hours. After the removal of solvent, a tube-like organosilicon polymer is obtained.
(1-2) In (2+2) mode of hydrosilylation coupling reaction, the synthetic procedure is as follows: An organo-bridged ladderlike polysiloxane having xe2x80x94CHxe2x95x90CH2 or xe2x80x94CH2xe2x80x94CHxe2x95x90CH2 side chains or having Sixe2x80x94H side chains is dissolved in dried solvent and is injected into a reaction apparatus under inert gas atmosphere. Then the solvent, Pt catalyst and the coupling reagent with terminal Sixe2x80x94H groups or terminal alkenyl or alkynyl groups are added to the reaction mixture. The concentration of reactants are in the range of 5xcx9c40 mg/mL. The molar ratio of ladderlike polysiloxane to the coupling reagent is 1:0.8 to 1:1.5. The reaction is carried out at 40xcx9c100xc2x0 C. for 12xcx9c72 hours. After the removal of solvent, a tube-like organosilicon polymer is obtained.
The Pt catalysts that can be used in the present invention for hydrosilylation reaction are H2PtCl6.6H2O or Cp2PtCl2.
The solvents that can be used in hydrosilylation reaction include toluene, xylene, ethylene glycol dimethyl ether, poly(allyl ether), dimethyl o-phthalate, 1,4-dioxane, tetrahydrofuran (THF), acetone, cyclohexanone or a mixture of above solvents. The amount of the solvent(s) is 50xcx9c500 mL/per gram of ladderlike polysiloxane.
The coupling agents having terminal alkenyl or alkynyl groups that can be used have the following structure: 
wherein n is 0, 1, or 2; m is 0 or 1; X is O, COO or is absent; Y is O, (CH3)2C or is absent.
The coupling reagents having Sixe2x80x94H group that can be used in the hydrosilylation reaction include the following 4 categories: 
(2) Diazo coupling reaction
The organo-bridged ladderlike polysiloxane having xe2x80x94C6H4OH or xe2x80x94C6H4xe2x80x94NH2 side groups is dissolved in inorganic or a mixture of inorganic and organic solvents. The concentration is 10xcx9c50 wt. %. The above solution is added to the reaction mixture. Then ice is added to the reaction mixture. The weight ratio of the ice to solvent is 1:3. Sodium acetate or acetic acid is added to the reaction mixture. The reaction is allowed to proceed at 0xcx9c5xc2x0 C. by ice-water. The organo-bridged ladderlike polysiloxane having diazo side groups in inorganic or a mixture of inorganic and organic solvents with a concentration of 10xcx9c50% is added dropwise to the flask under stirring. After the reaction, the reaction solution is extracted by diethyl ether. The ether solution was dried over anhydrous Na2SO4. After the removal of solvent, the tube-like organosilicon polymer is obtained in (1+1) mode.
The inorganic solvent or a mixture of inorganic and organic solvents that can be used in the diazo coupling reaction include water, mixture of water and alcohol, mixture of water and pyridine or mixture of water and acetic acid.
When using organo-bridged ladderlike polysiloxane having xe2x80x94C6H4OH side groups as the starting material during the diazo coupling reaction, the reaction should be carried out at weak base solution with a pH value of 8xcx9c10. When using organo-bridged ladderlike polysiloxane having xe2x80x94C6H4NH2 side groups as the starting material during the diazo coupling reaction, the reaction should be carried out at weak acid solution with a pH of 5xcx9c7.
The microstructure and chemical affinity of the tube-like organosilicon polymers derived from organo-bridged ladderlike polysiloxanes of the present invention can be readily adjusted (Table 1). Further, due to their solubility in organic solvents, the tube-like organosilicon polymers can be processed easily. These solvents include toluene, xylene, ethylene glycol dimethyl ether, poly(allyl ether), dimethyl o-phthalate, 1,4-dioxane, tetrahydrofuran (THF), acetone, cyclohexanone or a mixture of above solvents.
(3) Ulman or Grignard coupling reaction.
The organo-bridged ladderlike polysiloxane having xe2x80x94C6H4C6H4C6H4I or xe2x80x94C6H4C6H4Br side groups is dissolved in dried organic solvents under argon atmosphere. The concentration is 10xcx9c50 wt. %. Then the above solution is added dropwise to the reaction mixture containing Cu or Mg powders and a littler amount of I2 at 0xcx9cxe2x88x925xc2x0 C. The molar ratio of ladderlike polysiloxane to Cu or Mg powders is 1:1-1:5. The reaction is allowed to proceed at 0xcx9cxe2x88x925xc2x0 C. by ice-water for 2xcx9c5 hours and then warmed up gradually till reflux for 5xcx9c9 hours. The reaction solution is extracted with hexane after cooling. Then the hexane solution is dried over anhydrous Na2SO4. After the removal of solvent, a tube-like organosilicon polymer is obtained.
The organic solvents can be used in the Ulman or Grignard cyclization reaction include toluene, xylene, ethylene glycol dimethyl ether, poly(allyl ether), dimethyl o-phthalate, 1,4-dioxane, tetrahydrofuran (THF), acetone, cyclohexanone or a mixture of above solvents.
The properties are shown in Table 2.
The present invention further provides a tube-like organosilicon polymeric complex derived from the organo-bridged ladderlike polysiloxane of the present invention, which is represented by the following formula: 
Wherein,  is the low molar mass guest molecule, metal ion or polymer entrapped inside the tube.
The method for producing the tube-like organosilicon polymeric complexes of the present invention includes entrapping the guest molecules into the tube-like organosilicon polymers to form supermolecular complexes. Two methods can be used in performing the entrapment: in-situ entrapment and displacement entrapment. Guest molecules are either low molar mass molecules with functionality or metal ions.
The in-situ entrapment is referred to simultaneous tube formation and entrapment of the guest molecules. It is carried out according to the following procedures: During the tube-like organosilicon polymer formation process by one of the above-mentioned methods, guest molecules or ions are added in-situ. The weight of guest molecule iis 1xcx9c30 wt. % of that of tube-like organosilicon polymers. The reaction conditions are similar to those used above. When the tube-like polymers are formed the guest molecules possessing excellent molecular recognition ability (i.e. molecular dimension and chemical affinity) with tube-like polymers are simultaneously entrapped in-situ inside the tube to give the supermolecular complexes.
The structure of the organo-bridged ladderlike polysiloxane to be used is mentioned above.
The solvents may be used include toluene, xylene, ethylene glycol dimethyl ether, poly(allyl ether), dimethyl o-phthalate, 1,4-dioxane, tetrahydrofuran (THF), acetone, cyclohexanone, alcohols or a mixture of above solvents.
The displacement entrapment is performed according to the following procedures. The tube-like organosilicon polymers derived from the organo-bridged ladderlike polysiloxane and the guest molecules as mentioned above are dissolved in organic solvent(s). The weight of guest molecules is 1xcx9c20% of that of tube-like organosilicon polymers. The amount of the solvent used is 1xcx9c50 mL per gram of tube-like polymers. The guest molecules are entrapped inside the tube by ultrasonic (1 KHzxcx9c200 KHz), heating (20xcx9c200xc2x0 C.), or by changing the polarity of the solvent, to replace the solvent molecules or other molecules originally entrapped inside the tube.
The solvents that can be used include toluene, xylene, ethylene glycol dimethyl ether, poly(allyl ether), dimethyl o-phthalate, 1,4-dioxane, tetrahydrofuran (THF), acetone, cyclohexanone, alcohols or a mixture of above solvents.
The polymeric complexes of the present invention is soluble in a variety of solvents, therefore allows to be reprocessed. These solvents include toluene, xylene, ethylene glycol dimethyl ether, poly(allyl ether), dimethyl o-phthalate, 1,4-dioxane, tetrahydrofuran (THF), acetone, cyclohexanone, isopropanol, isobutanol, or a mixture thereof.